De Villiers has informed SA Rugby that he intends to play overseas at the end of the current Tri Nations series and needs only to secure an early release from his provincial contract with Western Province, which runs until 31 October, to complete the switch.
Western Province are already losing international back row man Luke Watson to Bath at the end of the Currie Cup campaign and the additional loss of De Villiers will be another huge blow to the Cape Town outfit.
Munster, the Heineken Cup champions in 2006 and 2008 and semi-finalists last season, have reaped the benefit of high profile overseas signings in the past. Springbok centre Trevor Halstead helped them to win Europe's top prize in 2006 and All Black legend Doug Howlett was in their 2008 winning side.
De Villiers will fill the hole in the Munster midfield vacated by former Maori centre Rua Tipoki and could find himself surrounded by two Lions in Ronan O'Gara and Keith Earls.